I'll second Anathem, The Great and Secret Show, and Angelmaker, though I'd expect all three to be somewhat divisive. All three have a strong postmodern bent to them, and I know some people are allergic.
The only recs I have left aren't exactly doorstops, but they're of respectable size:
The Bees by Laline Paul: Dark animal fantasy in the vein of Watership Down. The detail and immediacy of the bees' world is outstanding.
Queen City Jazz by Kathleen Ann Goonan: Just a page-turner fantasy journey set in a world transformed by a nanotech apocalypse. It did turn into a series, but was written and released as a standalone.
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